CN101623622A - Absorbent material and preparation thereof - Google Patents
Absorbent material and preparation thereof Download PDFInfo
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- CN101623622A CN101623622A CN200910055525A CN200910055525A CN101623622A CN 101623622 A CN101623622 A CN 101623622A CN 200910055525 A CN200910055525 A CN 200910055525A CN 200910055525 A CN200910055525 A CN 200910055525A CN 101623622 A CN101623622 A CN 101623622A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title abstract description 15
- 230000002745 absorbent Effects 0.000 title abstract 6
- 239000002250 absorbent Substances 0.000 title abstract 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- BPYKTIZUTYGOLE-IFADSCNNSA-N Bilirubin Chemical compound N1C(=O)C(C)=C(C=C)\C1=C\C1=C(C)C(CCC(O)=O)=C(CC2=C(C(C)=C(\C=C/3C(=C(C=C)C(=O)N\3)C)N2)CCC(O)=O)N1 BPYKTIZUTYGOLE-IFADSCNNSA-N 0.000 claims abstract description 52
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 239000011258 core-shell material Substances 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 3
- 239000002594 sorbent Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 239000004411 aluminium Substances 0.000 claims description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 11
- 150000005846 sugar alcohols Chemical class 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003463 adsorbent Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
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- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 20
- 239000000047 product Substances 0.000 description 13
- 230000010412 perfusion Effects 0.000 description 10
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- 238000005119 centrifugation Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
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- 238000005303 weighing Methods 0.000 description 2
- 208000037157 Azotemia Diseases 0.000 description 1
- 206010019663 Hepatic failure Diseases 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
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- HVHKMUMXERBUAN-IFADSCNNSA-N mesobilirubin IXalpha Chemical compound N1C(=O)C(CC)=C(C)\C1=C\C1=C(C)C(CCC(O)=O)=C(CC2=C(C(C)=C(\C=C/3C(=C(C)C(=O)N\3)CC)N2)CCC(O)=O)N1 HVHKMUMXERBUAN-IFADSCNNSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 230000002969 morbid Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
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- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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Abstract
The invention belongs to the field of nanomaterials, in particular to an absorbent material and a preparation thereof. The component of the absorbent material is amorphous carbon, and the absorbent material comprises a nano-mesoporous pore passage structure. The preparation method of the absorbent material comprises the following steps: preparation of an aluminum-doped mesoporous silica core-shell structural sphere, polymerization of furfuryl alcohol, carbonization and removal of a silica template. The absorbent material has higher saturated adsorption amount of bilirubin and very fast absorption rate, thereby being widely applied in the field of medical absorption.
Description
Technical field
The invention belongs to field of nanometer material technology, be specifically related to a kind of sorbent material and preparation thereof.
Background technology
Poisonous substance in the human body is divided into exogenous poisonous substance and endogenous poisonous substance two classes.The former is from the outer noxious material (as agricultural chemicals) of human body, when this noxious material is assembled the various pathologies that can cause health when too much at inside of human body; The latter then is the too much accumulation and can not effectively remove the time, the noxious material of formation (as bilirubin, uric acid etc.) also can cause various pathologies of the caused metabolin of human body self health fault.
Under normal circumstances, human body can pass through autoprotection system such as liver detoxification system, and human body self immune system and excretory system etc. are detoxified the endogenous or exogenous poisonous substance of removing or neutralize.But for acute drugs poisoning, uremia, diseases such as hepatic failure when human body self has lost detoxification ability, only use general internal medicine Clinical Processing (comprise gastric lavage, antagonism medicine etc. is used in transfusion) often to be difficult to prove effective.Event is adopted medical adsorbent to carry out blood perfusion and is purified the blood, and removes wherein to reach clinical therapeutic efficacy behind some morbid substance.
The cardinal principle of blood perfusion is exactly suction-operated.Blood perfusion has important effect with the development of sorbent material in the blood perfusion field, is the key factor of decision perfusion effect.Adsorbent commonly used at present mainly is active carbon, resin and polysaccharide material.Mostly the aperture is big owing to above-mentioned material, and pore-size distribution is inhomogeneous, and specific area is low etc., make its in various degree exist the rate of adsorption low, adsorbance is low wait not enough.Research and develop novel fast, high adsorption capacity and can realize that the sorbent material of perfusion device miniaturization is the actual requirement of blood purification treatment.
Meso-porous carbon material is the porous molecular sieve materials of class aperture between 2～50nm, and such material has single pore-size distribution, the meso-hole structure of high-sequential, high specific area and simple preparation technology, be chemistry always, material, the research focus of ambits such as medicine and biology.
The meso-porous carbon material Pyrogentisinic Acid, vitamin, protein and big molecular dye etc. has good adsorption property.But meso-porous carbon material also rarely has report both at home and abroad in the research aspect the medical sorbent material.
Summary of the invention
The object of the present invention is to provide a kind of sorbent material and preparation thereof.
The constituent of sorbent material of the present invention is an amorphous carbon, and this sorbent material has the mesoporous nano pore passage structure.
Preferably, described mesopore orbit structure is the orderly or unordered mesopore orbit structure of 2～4.5nm.
The mesopore orbit preferred, that described mesopore orbit structure is interlinked to the outside in being.
Preferably, the specific area of described sorbent material is 700～1200m
2/ g, pore volume are 0.98～1.2cm
3/ g.
Preferred, the microscopic particles of described sorbent material is shaped as sphere, and the particle diameter of this microscopic particles is 80 ~ 300nm.
The preparation method of sorbent material of the present invention comprises the steps: to mix the removal of preparation, furfuryl alcohol polymerization, carbonization and the silica template of aluminium meso-porous silica core-shell structure ball.
Preferably, the described particle diameter of mixing aluminium meso-porous silica core-shell structure ball is 80～300nm.
Described preparation process of mixing aluminium meso-porous silica core-shell structure ball is: ammoniacal liquor, absolute ethyl alcohol and deionized water are made initial reaction solution, in initial reaction solution, after adding ethyl orthosilicate under 25～45 ℃ the temperature conditions, stir, the mixed solution that adds ethyl orthosilicate and octadecyl trimethoxy silane then, and with after the product separation, make after reacting behind the adding aluminum sulfate solution through washing, drying and calcining.
Preferably, in the described initial reaction solution, the volume ratio of ammoniacal liquor, absolute ethyl alcohol and deionized water is 0.08～1.6: 2～36: 1.
The concentration of described ammoniacal liquor is not limit, and is preferably mass percent and is 14%～30% ammoniacal liquor.
Preferably, the volume ratio of described initial reaction solution and ethyl orthosilicate is: 9.5～35.5: 1.
Preferably, in the mixed solution of described ethyl orthosilicate and octadecyl trimethoxy silane, the volume ratio of ethyl orthosilicate and octadecyl trimethoxy silane is: 1.3～4: 1.
Preferably, the volume ratio of the mixed solution of described initial reaction solution and ethyl orthosilicate and octadecyl trimethoxy silane is: 6.3～38.8: 1.
Preferably, in the described aluminum sulfate solution, the molal volume concentration of aluminum sulfate is 0.15～0.60mol/L.
Preferably, the volume ratio of described initial reaction solution and aluminum sulfate solution is: 57～213: 1.
Preferably, described mixing time is 20～120min.
Preferably, the reaction time behind the described adding aluminum sulfate solution is 20～120min.
Preferably, described calcining heat is 450～700 ℃, and more preferably 550 ℃, calcination time is 1～6h.
Most preferred, described preparation process of mixing aluminium meso-porous silica core-shell structure ball is: with 2～～ammoniacal liquor of 8mL, 50～～after the absolute ethyl alcohol of 180mL and the deionized water of 5～25mL mix, after adding the 6mL ethyl orthosilicate between 25～45 ℃, stirring 20～120min; The mixed liquor that adds the octadecyl trimethoxy silane of the ethyl orthosilicate of 4～6mL and 1.5～3mL then, and the aluminum sulfate solution of 1mL 0.15～0.60mol/L continue reaction 20～120min; After product separated, under 550 ℃ condition, calcine 1～6h after spending the deionised water drying.
Described furfuryl alcohol step of polymerization is: adopt the mode that drips that sugar alcohol is splashed into and mix in the aluminium meso-porous silica core-shell structure ball powder, then the powder after the above-mentioned dropping is carried out the sugar alcohol polymerisation under vacuum condition.
Preferably, described rate of addition is 0.2～0.5mL/min.
Preferably, described ratio of mixing aluminium meso-porous silica core-shell structure ball powder and sugar alcohol is: every 1g mixes the sugar alcohol that drips 0.8～1.6ml in the aluminium meso-porous silica core-shell structure ball.
Preferably, the reaction temperature of described sugar alcohol polymerisation is 55～80 ℃, and the reaction time is 2～5h.
Preferably, described sugar alcohol polymerisation need be evaporated 8～24h after finishing under vacuum condition.The purpose of vacuum evaporation is to remove unpolymerized sugar alcohol.
Described carburising step is: under the protective atmosphere, will be under 600～1000 ℃ temperature conditions through the sugar alcohol polymerization mix aluminium meso-porous silica core-shell structure ball heat treatment 3～6h.
Preferably, described protective atmosphere is a nitrogen atmosphere.
The removal step of described silica template is: mix aluminium meso-porous silica core-shell structure ball powder with the washing of 70～100 ℃ strong base solutions after carbonization.
Preferably, also need separated product after the removal of described silica template, wash then and drying.
Preferably, described strong base solution is that concentration is the NaOH aqueous solution of 2M.
Sorbent material of the present invention adopts following steps to carry out adsorption test:
(1) preparation of bilirubin solution:
Weighing 250mg bilirubin under the lucifuge with the NaOH solution dissolving of a spot of 0.2mol/L, is transferred to solution in the volumetric flask of 250mL earlier again, is settled to graduation mark with the sodium hydrogen phosphate of PH=7.4 and the cushioning liquid of sodium dihydrogen phosphate (PBS).By dilution, can prepare the bilirubin adsorption liquid of required various concentration at last.
(2) adsorption process and adsorbance are calculated:
Accurately take by weighing the sorbent material 0.05g of above-mentioned preparation, join in the 20mL bilirubin adsorption liquid.Mixed liquor is stirred (needing lucifuge) under constant temperature, behind the certain hour, get a certain amount of supernatant liquor, measure the absorbance under the bilirubin characteristic absorption wavelength and obtain its concentration with filter membrane.Adsorbance Q (mg/g) is calculated by following equation:
Q(mg/g)＝(C
0-C
t)V/1000W；
C in the formula
0And C
tBe respectively the concentration (mg/L) of absorption front and back solution mesobilirubin, W is meso-porous hollow carbon sphere or activated carbon powder body weight (g), and V is adsorption liquid volume (mL).
Sorbent material of the present invention can be used as medical adsorbent, especially bilirubin is had very high saturated extent of adsorption (being commercial with more than 4 times of perfusion level charcoal absorption amount), and the rate of adsorption very fast (bilirubin concentration just has rapid decline during absorption 2min).The adsorbent that this sorbent material can be used as adsorbing bilirubin is applied in the blood purification, on the adsorbance and the rate of adsorption, have a clear superiority in active carbon than existing perfusion, help to reduce the blood perfusion time and reduce the adsorbent use amount, thereby alleviate patient's slight illness and treatment cost.
Description of drawings
The transmission electron microscope photo of the sorbent material that makes among Fig. 1: the embodiment 1 (unordered mesoporous).
The sorbent material adsorbing bilirubin solution concentration that makes among Fig. 2: the embodiment 1 is curve over time.
The sorbent material adsorbing bilirubin amount that makes among Fig. 3: the embodiment 1 is with the change curve of bilirubin concentration.
Fig. 4: commercial perfusion level charcoal absorption bilirubin solution concentration is curve over time.
Fig. 5: commercial perfusion level charcoal absorption bilirubin amount is with the change curve of bilirubin concentration.
The specific embodiment
Further specify the present invention below by embodiment and Comparative Examples.
Embodiment 1
The preparation of sorbent material:
What at first prepare 260～280nm size mixes aluminium meso-porous silica core-shell ball: 6.28mL ammoniacal liquor, and the absolute ethyl alcohol of 74mL and the deionized water of 10mL are stirring 1h at 30 ℃ after adding the 6mL ethyl orthosilicate down; The octadecyl trimethoxy silane that adds 5mL ethyl orthosilicate and 2mL then, and concentration is the aluminum sulfate aqueous solution 1mL continuation reaction 1h of 0.45mol/L; With the product centrifugation, after washing and the drying, calcine 6h down for 550 ℃ and remove template, make the meso-porous silica core-shell ball of mixing aluminium thus.
Get above-mentioned powder 0.5g and put into small beaker, the furfuryl alcohol of 0.6mL is splashed into powder with the speed of 0.3mL/min, make the abundant wetting powder of furfuryl alcohol; After then small beaker being put into 60 ℃ vacuum drying oven heating 3h, begin to vacuumize, and keep vacuum state 10h; The powder of gained is put into atmosphere furnace, be raised to 600 ℃ of insulation 4h with the speed among the 2 ℃/min, whole carbonisation carries out under nitrogen atmosphere.The gained powder, separates at 85 ℃ of removing templates twice that go down then through 2M NaOH solution, and washing and drying have just obtained target product.Prepared meso-porous hollow carbon sphere (260 ~ 280nm) specific area: 735.6m
2/ g, pore size: 3.7nm, pore volume: 0.98cm
3/ g.
Embodiment 2
The preparation of sorbent material:
According to technological process described (with embodiment 1), what at first prepare 160～180nm size mixes aluminium meso-porous silica core-shell ball: 3.14mL ammoniacal liquor, and the absolute ethyl alcohol of 74mL and the deionized water of 10mL are stirring 1h at 30 ℃ after adding the 6mL ethyl orthosilicate down; The octadecyl trimethoxy silane that adds 5mL ethyl orthosilicate and 2mL then, and concentration is the aluminum sulfate aqueous solution 1mL continuation reaction 1h of 0.45mol/L; With the product centrifugation, after washing and the drying, calcine 6h down for 550 ℃ and remove template, make the meso-porous silica core-shell ball of mixing aluminium thus.Get above-mentioned powder 0.5g and put into small beaker, the furfuryl alcohol of 0.6mL is splashed into powder with the speed of 0.3mL/min, make the abundant wetting powder of furfuryl alcohol; After then small beaker being put into 60 ℃ vacuum drying oven heating 3h, begin to vacuumize, and keep vacuum state 10h; The powder of gained is put into atmosphere furnace, be raised to 600 ℃ of insulation 4h with the speed among the 2 ℃/min, whole carbonisation carries out under nitrogen atmosphere.The gained powder, separates at 85 ℃ of removing templates twice that go down then through 2M NaOH solution, and washing and drying have just obtained target product.The specific area of prepared meso-porous hollow carbon sphere: 769.5m
2/ g, pore size: 3.8nm, pore volume: 1.00cm
3/ g.
Embodiment 3
The preparation of sorbent material:
What at first prepare 80～100nm size mixes aluminium meso-porous silica core-shell ball: 2mL ammoniacal liquor (mass percent is 30%), and the absolute ethyl alcohol of 180mL and the deionized water of 25mL are stirring 20min at 25 ℃ after adding the 6mL ethyl orthosilicate down; The octadecyl trimethoxy silane that adds 4mL ethyl orthosilicate and 1.5mL then, and concentration is the aluminum sulfate aqueous solution 1mL continuation reaction 2h of 0.15mol/L; With the product centrifugation, after washing and the drying, calcine 4h down for 450 ℃ and remove template, make the meso-porous silica core-shell ball of mixing aluminium thus.
Get above-mentioned powder 0.5g and put into small beaker, the furfuryl alcohol of 0.8mL is splashed into powder with the speed of 0.2mL/min, make the abundant wetting powder of furfuryl alcohol; After then small beaker being put into 55 ℃ vacuum drying oven heating 5h, vacuum state is evaporation 24h down; The powder of gained is put into atmosphere furnace, be raised to 1000 ℃ of insulation 3h with the speed among the 2 ℃/min, whole carbonisation carries out under nitrogen atmosphere.The gained powder, separates at 85 ℃ of removing templates twice that go down then through 2M NaOH solution, and washing and drying have just obtained target product.The specific area of prepared meso-porous hollow carbon sphere: 700m
2/ g, pore size: 2nm, pore volume: 1.2cm
3/ g.
Embodiment 4
The preparation of sorbent material:
What at first prepare 280～300nm size mixes aluminium meso-porous silica core-shell ball: 8mL ammoniacal liquor (mass percent is 14%), and the absolute ethyl alcohol of 50mL and the deionized water of 5mL are stirring 120min at 45 ℃ after adding the 6mL ethyl orthosilicate down; The octadecyl trimethoxy silane that adds 6mL ethyl orthosilicate and 3mL then, and concentration is the aluminum sulfate aqueous solution 1mL continuation reaction 20min of 0.60mol/L; With the product centrifugation, after washing and the drying, calcine 1h down for 700 ℃ and remove template, make the meso-porous silica core-shell ball of mixing aluminium thus.
Get above-mentioned powder 0.5g and put into small beaker, the furfuryl alcohol of 0.4mL is splashed into powder with the speed of 0.5mL/min, make the abundant wetting powder of furfuryl alcohol; After then small beaker being put into 80 ℃ vacuum drying oven heating 2h, vacuum state is evaporation 8h down; The powder of gained is put into atmosphere furnace, be raised to 720 ℃ of insulation 4.5h with the speed among the 2 ℃/min, whole carbonisation carries out under nitrogen atmosphere.The gained powder, separates at 85 ℃ of removing templates twice that go down then through 2M NaOH solution, and washing and drying have just obtained target product.The specific area of prepared meso-porous hollow carbon sphere: 1200m
2/ g, pore size: 4.5nm, pore volume: 1.2cm
3/ g.
Embodiment 5
The preparation of sorbent material:
Mix the preparation of aluminium meso-porous silica core-shell ball: 6mL ammoniacal liquor, the absolute ethyl alcohol of 100mL and the deionized water of 15mL stir 90min behind the adding 6mL ethyl orthosilicate down at 40 ℃; The octadecyl trimethoxy silane that adds 5mL ethyl orthosilicate and 2mL then, and concentration is the aluminum sulfate aqueous solution 1mL continuation reaction 80min of 0.45mol/L; With the product centrifugation, after washing and the drying, calcine 4h down for 550 ℃ and remove template, make the meso-porous silica core-shell ball of mixing aluminium thus.
Get above-mentioned powder 0.5g and put into small beaker, the furfuryl alcohol of 0.5mL is splashed into powder with the speed of 0.4mL/min, make the abundant wetting powder of furfuryl alcohol; After then small beaker being put into 65 ℃ vacuum drying oven heating 3h, vacuum state is evaporation 16h down; The powder of gained is put into atmosphere furnace, be raised to 850 ℃ of insulation 4h with the speed among the 2 ℃/min, whole carbonisation carries out under nitrogen atmosphere.The gained powder, separates at 85 ℃ of removing templates twice that go down then through 2M NaOH solution, and washing and drying have just obtained target product.
Embodiment 6
The meso-porous hollow carbon sphere that makes among the embodiment 1 is used for bilirubinic absorption.The pattern directly perceived of this meso-porous hollow carbon sphere is seen Fig. 1, and its dependency structure parameter is: specific area: 769.5m
2/ g, pore size: 3.8nm, pore volume: 1.00cm
3/ g.By investigate bilirubin solution concentration (initial concentration is 250mg/g) with the variation of meso-porous hollow carbon sphere (0.1g) adsorption time as seen, promptly reach balance behind the absorption 30min, bilirubin concentration sharply descends (as shown in Figure 2) behind absorption 2min.By the equilibrium adsorption of meso-porous hollow carbon sphere (0.05g) to the bilirubin solution of variable concentrations, the adsorbance of investigating meso-porous hollow carbon sphere with the variation of bilirubin solution concentration can this meso-porous hollow carbon sphere saturated adsorption capacity reach 302mg/g.
The performance of the adsorbent that makes among embodiment 7 commercially available perfusion level active carbons and the embodiment 1 relatively.
Adopt commercial now perfusion level active carbon (originating from Langfang, Hebei Ai Er blood purification equipment factory) that bilirubin is adsorbed.This perfusion level active carbon specific area is: 803.9m
2/ g; Pore volume is: 0.31cm
3/ g.By investigating bilirubin solution concentration (initial concentration is 250mg/g) as seen with the variation of active carbon (0.1g) adsorption time, just reach balance behind the absorption 300min, bilirubin concentration changes (as shown in Figure 4) gently in time.By the equilibrium adsorption of active carbon (0.1g) to the bilirubin solution of variable concentrations, the adsorbance of investigating active carbon with the variation of bilirubin solution concentration can this active carbon saturated adsorption capacity be about 70mg/g (as shown in Figure 5).By this contrast test as can be known: the adsorbent that makes among the embodiment 1 is compared with active carbon with existing perfusion, and bigger to bilirubinic saturated extent of adsorption, the rate of adsorption is faster.
Claims (10)
1, a kind of sorbent material, the constituent of this sorbent material are amorphous carbon, and this sorbent material has the mesoporous nano pore passage structure.
2, the sorbent material described in claim 1 is characterized in that, the particle diameter of the microscopic particles of described sorbent material is 80～300nm, the mesopore orbit structure that described mesoporous nano pore passage structure is 2～4.5nm.
As the described sorbent material of arbitrary claim in claim 1 or 2, it is characterized in that 3, the specific area of described sorbent material is 700～1200m
2/ g, pore volume are 0.98～1.2cm
3/ g.
4, the preparation method of the described sorbent material of arbitrary claim in the claim 1～3, the removal that comprises the steps: to mix preparation, furfuryl alcohol polymerization, carbonization and the silica template of aluminium meso-porous silica core-shell structure ball.
5, the preparation method of the sorbent material described in claim 4, it is characterized in that, described preparation process of mixing aluminium meso-porous silica core-shell structure ball is: ammoniacal liquor, absolute ethyl alcohol and deionized water are made initial reaction solution, in initial reaction solution, after adding ethyl orthosilicate under 25～45 ℃ the temperature conditions, stir, the mixed solution that adds ethyl orthosilicate and octadecyl trimethoxy silane then, and with after the product separation, make after reacting behind the adding aluminum sulfate solution through washing, drying and calcining.
6, the preparation method of the sorbent material described in claim 4, it is characterized in that, described furfuryl alcohol step of polymerization is: adopt the mode that drips that sugar alcohol is splashed into and mix in the aluminium meso-porous silica core-shell structure ball powder, then the powder after the above-mentioned dropping is carried out the sugar alcohol polymerisation under vacuum condition.
7, the preparation method of the sorbent material described in claim 4; it is characterized in that; described carburising step is: under the protective atmosphere, will be under 600～1000 ℃ temperature conditions through the sugar alcohol polymerization mix aluminium meso-porous silica core-shell structure ball heat treatment 3～6h.
8, the preparation method of the sorbent material described in claim 4 is characterized in that, the removal step of described silica template is: mix aluminium meso-porous silica core-shell structure ball powder with the washing of 70～100 ℃ strong base solutions after carbonization.
9, the described sorbent material of arbitrary claim is used as medical adsorbent in the claim 1～3.
10, the described sorbent material of arbitrary claim is used for adsorbing bilirubin in the claim 1～3.
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| CN102389771A (en) * | 2011-10-17 | 2012-03-28 | 江苏大学 | Method for preparing bell type magnetic mesoporous silica-microsphere absorbent |
| CN102728330A (en) * | 2012-06-29 | 2012-10-17 | 杭州电子科技大学 | Preparation method for carbon nanometer material with adsorption performance |
| CN103055822A (en) * | 2011-10-21 | 2013-04-24 | 佛山市博新生物科技有限公司 | Blood-purifying adsorbent for clearing blood bilirubin and preparation method thereof |
| CN103785355A (en) * | 2012-11-02 | 2014-05-14 | 中国科学院上海硅酸盐研究所 | Mesoporous/macropore hierarchical pore block bilirubin adsorbent material and preparation method thereof |
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| CN100364884C (en) * | 2006-01-26 | 2008-01-30 | 复旦大学 | Method for preparing mesoporous carbon material |
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| CN102728330A (en) * | 2012-06-29 | 2012-10-17 | 杭州电子科技大学 | Preparation method for carbon nanometer material with adsorption performance |
| CN102728330B (en) * | 2012-06-29 | 2013-11-06 | 杭州电子科技大学 | Preparation method for carbon nanometer material with adsorption performance |
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| CN105126787A (en) * | 2015-08-03 | 2015-12-09 | 佛山市博新生物科技有限公司 | Method for improving anticoagulant activity of adsorbent |
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| CN105688811A (en) * | 2016-02-03 | 2016-06-22 | 青岛安布雷拉环保科技有限公司 | Pure gas-gathering tower type spherical diatomite particle purifying adsorbent and preparation method thereof |
| CN110385107A (en) * | 2018-04-17 | 2019-10-29 | 中国科学院大连化学物理研究所 | A kind of hydrophily adsorbent for bilirubin and its preparation and application |
| CN110385107B (en) * | 2018-04-17 | 2021-09-14 | 中国科学院大连化学物理研究所 | Hydrophilic bilirubin adsorbent and preparation and application thereof |
| CN116571206A (en) * | 2023-04-27 | 2023-08-11 | 湖北三峡实验室 | Aluminum-containing silicon-based adsorbent, preparation method thereof and application of adsorbent in removing glyphosate in water |
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